Preparation of nitroketonized amides

ABSTRACT

A method of preparing a nitroketonized amide by contacting an acid amide of the formula:   WHERE R1 is an alkenyl group of from 4 to 40 carbon atoms, where R2 and R3 alternately represent hydrogen and an alkenoyl group of from 4 to 40 carbon atoms, with dinitrogen tetroxide and oxygen, at mole ratios of acid amide to dinitrogen tetroxide to oxygen of from 1:2:2 to 1:4:60.

United States Patent Lachowicz et al. June 3, 1975 [54] PREPARATION OF TZED 3,746,729 7/1973 Lachowicz 260/4045 AMIDES P E L G rimary xaminerewis otts [75] Inventors 3 5' fi gl if fr gg Assistant ExaminerEthel G.Love t a 1s Attorney, Agent, or FirmT. H. Whaley; C. G. Ries; appmgers aa 0 George J. Darsa [73] Assignee: Texaco Inc., New York, NY. [57]-ABSTRACT [22] Fil d; J l 10, 1972 A method of preparing a nitroketonizedamide by con- [21] pp No: 270,362 tactlng an acid amide of the formula:

Related U.S. Application Data 1 N CH2 CH2 CH2 N H [62] Division of Ser.No. 101,408, Dec. 24, 1970, Pat. No. 2 3

[52] U.S. Cl 260/4045; 44/7]; 260/561 K; where R is an alkenyl group offrom 4 to 40 carb 260/561 N atoms, where R and R alternately representhydro- [51] Int. Cl. C07c 103/30 g n n n alkenoyl group of from 4 to 40carbon [58] Field of Search 260/4045, 561 K atoms, i h n rog n etroxideand oxygen, at mole ratios of acid amide to dinitrogen tetroxide tooxygen References Cited of from 1:222 to 1:4:60.

UNITED STATES PATENTS 8 Claims, No Drawings 3,458,582 7/1969 Lachowiczet al 260/4045 X 1 PREPARATION OF NITROKETONIZED AMIDES This is adivision of application Ser. No. 101,408, filed Dec. 24, 1970, now US.Pat. No. 3,711,255.

BACKGROUND OF THE INVENTION This invention relates to an improved motorfuel composition for internal combustion engines. More particularly, theinvention involves the discovery that the incorporation of a minoramount of a nitroketonized amide into gasoline produces a fuel havingimproved carburetor detergent properties along with good corrosioninhibiting and anti-icing properties.

Modern internal combustion engine design is undergoing significantchanges to meet higher standards concerning engine and exhaust gasemissions. A major change in engine design presently being widelyadopted is the feeding of crankcase blow-by gases of the engine into theintake air supply to the carburetor rather than venting to theatmosphere as was done in the past. Blow-by gases, however, containsubstantial amounts of deposit-forming substances and it has beenobserved that some of the constituents in the blow-by gas form depositsin and around the throttle plate area of the carburetor. Such depositsrestrict the flow of air through the carburetor at idle and low speedsresulting in an overrich fuel mixture. Such a condition produces roughidling, engine stalling and also results in excessive hydrocarbonexhaust emissions to the atmosphere. In addition to overcoming theforegoing problem, a competitive modern gasoline must provide a highdegree of corrosion inhibiting and anti-icing properties.

A novel fuel composition has been discovered which mitigates orovercomes the problem of deposit laydown in the carburetor of aninternal combustion engine. More specifically, a motor fuel compositioncontaining a novel additive has been found which is effective forsubstantially reducing the laydown of deposits in a carburetor. Theadditive also provides excellent corrosion inhibiting and anti-icingproperties in the gasoline.

Broadly, this invention contemplates a motor fuel composition comprisinga mixture of hydrocarbons in the gasoline boiling range and a minoramount of a nitroketonized amide corresponding to the formula:

R Ill CH -Ch CH where R is an alkyl, alkenyl, nitroketonized alkyl ornitroketonized alkenyl group, where R and R alternately representhydrogen and an alkanoyl, alkenoyl, nitroketonized alkanoyl ornitroketonized alkenoyl group, wherein at least one of said R, R or R"is a nitroketonized group as heretofore defined. In particular, R whenalkyl represents a group having from 1 to 40, preferably 8 to 22, carbonatoms and when alkenyl, nitroketonized alkyl or nitroketonized alkenylrepresents a group having from 4 to 40, preferably 8 to 22, carbonatoms. Further, R and R when alternately representing a group recitedabove, other than hydrogen, contains from 4 to 40, preferably 8 to 22,carbon atoms. The nitroketonized amides employed in this invention areprepared by contacting the precursor, namely an acid amide, of theformula:

where R is an alkyl group having from 1 to 40 carbon atoms or alkenylgroup having from 4 to 40 carbon atoms, where R and R alternatelyrepresent hydrogen and an alkanoyl group or an alkenoyl group havingfrom 4 to 40 carbonatoms, wherein at least one of said R, R orR isanalkenyl or an alkenoyl group, with dinitrogen tetroxide and oxygen ata temperature of from about 35 to 45C. in a mole ratio of said acidamide to dinitrogen tetroxide to oxygen of from 1:1:1 and 1:4:60. In adesirable embodiment R and R or R are respectively alkenyl and alkenoylgroups having from 4 to 40, preferably 8 to 22, carbon atoms and wherethe mole ratio of acid amide to dinitrogen tetroxide to oxygen is from1:22 to 1:4:60. Preferably, the reaction is conducted at temperatures offrom 10 to 30C. and R, R or R represent groups having from 8 to 22carbon atoms.

Nitroketonization of the afroementioned acid amide can be accomplishedin a one-step reaction as contrasted to other known processes whereolefins are initially converted to intermediate nitroperoxy compoundsand where the intermediate compound is subsequently contacted with adenitrating agent to yield a nitroketone product. Here, the introductionof a denitrating agent is not essential inasmuch as autogenousconversion at the point of unsaturation directly results in vicinalnitroketonization.

The acid amide containing at least one group identified as R, R or Rpossessing at least one unsaturated (-Cl-l CH) group along a carbonchain is converted in the course of nitroketonization to a vicinalnitroketone function N02 0 l 11 (-CH c For example, unsaturation of theacid amide may be in R as an alkenyl group such as 3-buteny1,Z-pentenyl, lO-undecenyl, 9-octadecenyl and 13-docosenyl. AlternativelyR may be an alkyl group such as methyl, ethyl, butyl, hexyl, dodecyl,hexadecyl and tetracosanyl. When R is alkyl unsaturation of the acidamide occurs at R or R as an alkenoyl group such as 2-methyl-3-butenoyl, 3-butenoyl, l0 undecenoyl, 8-hexadecenoyl, 9-octadecenoy1 andl3-docosenoy1. Alternatively when R or R is alkanoyl, such asisobutanoyl, heptanoyl, decanoyl, pentadecanoyl and tetracosanoyl, R isan alkenyl group. Further, unsaturation may occur in a plurality ofpoints along R, R or R Moreover, unsaturation at one or more points mayoccur simultaneously in R and R or R as when R is 9-octadecenyl and R orR is 10-undecenoyl. Depending on the ratio of acid amide to dinitrogentetroxide to oxygen, acid amides having a plurality of unsaturatedlinkages can to varying degrees be singularly to totally converted tovicinal nitroketone groups. Where a plurality of unsaturation occurs andit is contemplated that some or all be converted to vicinal nitroketonegroups the lower ratios of acid amide to dinitrogen tetroxide to oxygenof 1:212 to 124260 are employed along with a denitrating agentintroduced to the reaction product resulting from contacting of the acidamide, dinitrogen tetroxide and oxygen.

The denitrating agent is added to the reaction product in a mole ratioof agent to product of at least 1:1 and preferably less than about 20:1at a temperature about 35 to 45C. Specific examples of denitratingagents include dimethylformamide, diethylformamide, dimethylacetamide,dimethylsulfoxide, diethylsulfoxide, tetramethylurea and tetraethylurea.

When unsaturation of R R or R occurs internally, that is, on other thana terminal carbon atom, the reaction yields a mixture of two isomericvicinal nitroketonized amides, illustratively, N-( 9-nitroloctadecanonyl)-N '-octadecanoyll ,3-diaminopropane and N-(l0-nitro-9-octadecanonyl)-N'-octadecanoyl- 1,3-diaminopropane. Whenunsaturation occurs be tween the terminal and adjacent carbon atom,nitration occurs on the terminal carbon and ketonization on the carbonvicinal thereto as for example N-decyl-N-(4- nitro-3-butanonyl)1,3-diaminopropane.

The unsaturated acid amide employed as a starting reactant is preparedfrom readily available materials. Essentially, such an acid amide isprovided by reacting primary amine with acrylonitrile to yield thecorresponding N-( 2-cyanoethyl-N-alkylamine and subsequently selectivelyhydrogenating the cyano group to the N-hydrocarbyl-l,3-diaminopropane (adiamine) where the hydrocarbyl radical is alkyl or alkenyl.Subsequently, the N-hydrocarbyl-l ,3-diaminopropane is reacted with a Cto C alkanoic or alkenoic acid to form an ammonium salt of the acidwhich upon heating in the absence of added water is converted to theacid amide. With regard to the alkenyl or alkenoyl group, each may haveone or more points of unsaturation that subsequently undergonitrokentonization according to the process herein described. Forexample, polyunsaturated acids as those occurring in whale oil, fishoil, corn oil, linseed oil and other oils can be employed including9,12-octadecadienoic acid and 9,12,15- octadecatrienoic acid.

In the course of nitroketonization of the acid amide, air can beemployed as the source of oxygen or oxygen can be provided in admixturewith inert gases such as nitrogen or argon. Under preferred conditions,oxygen and dinitrogen tetroxide are respectively introduced into thereaction zone containing the amide at a rate of between 1 and 16milliliters per minute of oxygen per gram of amide and between about0.005 and 0.05 grams of dinitrogen tetroxide per minute per gram ofamide. Atmospheric and higher pressures may be employed and the reactionis conveniently conducted in the presence of inert organic solventshaving from 4 to 22 carbon atoms exemplified by hydrocarbons includingparaffins such as pentane, hexane, octane, decane, dodecane, octadecane;cycloparaffins such as cyclopentane and cyclohexane; and aromatichydrocarbons such as benzene and toluene. In general, reaction times ofabout one-half to ten hours are employed, the time related to the rateof addition of the dinitrogen tetroxide.

It is to be noted that the dinitrogen tetroxide employed is actually anequilibrium mixture of dinitrogen tetroxide and nitrogen dioxide withthe equilibrium being driven to essentially 100 percent dinitrogentetroxide at 0C. and essentially 100 percent nitrogen dioxide at 140C.at 1 atmosphere pressure.

Nitroketonized amides contemplated as motor fuel additives hereininclude by way of illustration and not limitationN-hexyl-N'-(9-nitro-l0-octadecanonoyl)-1,3-

diaminopropane,

N-hexyl-N-( l0-nitro-9-octadecanonoyl)-l ,3-

diaminopropane,

N-hexyl-N-(9-nitrol 0-octadecanonoyl l ,3-

diaminopropane,

N-hexyl-N-(10-nitro-9-octadecanonoyl)-l,3-

diaminopropane,

N-(9-nitrol 0-octadecanonyl )-N'-heptanoyll ,3-

diaminopropane,

N-( 10-nitro-9-octadecanonyl)-N-heptanoyl-l ,3-

diaminopropane,

N-( 13-nitro-l4-docosanonyl)-N'-(8-hexadecenoyl)- l ,3-diaminopropane,

N-( l4-nitro- 1 3-docosanonyl)-N 8-hexadecenoyl)- 1 ,3-diaminopropane,

N-( l3-docosenyl)-N'-(8-nitro-9-hexadecanonoyl)-l ,3-

diaminopropane,

N-( l 3-docosenyl)-N-(9-nitro-8-hexadecanonoyl)-l ,3-

diaminopropane,

N-(13-nitro-l4-docosanonyl)-N'-(8-nitro-9- hexadecanonoyl)-l,3-diaminopropane and N-( 14- nitro-l 3-docosanonoyl )-N-( 8-nitro-9-hexadecanonoyl)-l ,S-diaminopropane.

In general, effective detergent motor fuels are produced by adding fromabout 0.0001 to 0.1 weight percent of the nitroketonized amide to thegasoline. A preferred concentration of the nitroketonized amide is inthe range from about 0.001 to 0.02 weight percent which corresponds toabout 3 to 60 PTB (pounds of additive per 1000 barrels of fuel).

The carburetor detergency effect of the additive and motor fuelscontaining the same was determined in a specially developed engine testdesignated the Chevrolet V-8 Carburetor Detergency Test. This test wasconducted using a Chevrolet V-8 engine equipped with a 4-barrelcarburetor mounted on a test stand. The two secondary barrels of thecarburetor were sealed and each of the primary barrels arranged so thatan additive fuel could be run in one barrel and a base fuel run in theother. The primary carburetor barrels were modified to the extent thatthey had removable aluminum inserts in the throttle plate area so thatdeposits formed in this area could be conveniently weighed.

In the test designed to determine the effectiveness of thedetergent-containing fuel for preventing the laydown of deposits, theengine is run for a period of 24 to 48 hours with the base fuel beingfed to one barrel and the additive fuel to the other barrel while engineblow-by is circulated to the air inlet of the carburetor. After the run,the inserts are removed from the carburetor and weighed to determine thedifference between the performance of the additive and non-additivefuels. The aluminum inserts are then cleaned, replaced in the carburetorand the process repeated with the fuels reversed in the carburetorbarrels to minimize differences in fuel distribution and barrelconstruction. The deposit weights in the two runs are averaged and thedetergency effectiveness of the additive fuel expressed in percent.

The anti-icing properties of the additive-containing fuel of theinvention was determined in a carburetor icing demonstrator apparatusconsisting of a vacuum pump equipped so that cool moisture-saturated airfrom an ice tower is drawn through a sample glass tube gasolinecarburetor. The gasoline sample is placed in a sample bottle and isdrawn into the glass carburetor Y 1 through a 20 gage hypodermic needle.Evaporation of the gasoline in the gas tube further cools the cold moistair with resulting ice formation on the throttle plate. The formation ofice on the throttle plate causes an engine to stall and it has beenfound that this condition is equivalent to a pressure drop across thethrottle plate of about 0.5 inches and 0.9 inches of mercury and thetime required to reach this pressure drop is noted. The vacuum pump isadjusted to give a vacuum of 1.8 inches of mercury and the test is rununtil either a pressure of 2.3 inches mercury has been reached or therun has continued for 300 seconds. Since, with most fuels, this pressuredrop is reached in l to 4 minutes 300 seconds is the maximum time for arun. A fuel composition which provides a minimum of 200 seconds runin'this test is an effective carburetor anti-icing fuel composition.

The anti-rusting properties of motor fuels was determined by insertingand thoroughly wetting a cold-rolled steel strip into a tall form fourounce glass bottle containing 90 cc of the fuel sample and adding 20 ccof distilled water. The bottle was stoppered, agitated for 15 secondsand stored at room temperature for 24 hours. The strip was thereaftervisually inspected and the percentage of rusted surface area estimated.

In order to more fully illustrate the nature of this invention andmanner of practicing the same, the following examples are presented.

EXAMPLE I To a solution of 14.7 grams (0.025 mole) of a mixture ofN-(9-octadecenyl)-N-(9-octadecenoyl)-1,3- diaminopropane andN-(9-octadecenyl)-N-(9- octadecenoyl)-l,3-diaminopropane in 200 ml. ofnhexane as inert solvent, there was added simultaneously oxygen at arate of 60.8 milliliters per minute and dinitrogen tetroxide at the rateof 0.0081 moles per hour for 3.1 hours at 0C. After 3.1 hours, 1.5milliliters of liquid dinitrogen tetroxide (0.025 mole) has beentransferred to the reaction flask and the solution was purged withoxygen for about 1 hour. The reaction mixture was washed with 150 ml. of3.3% aqueous sodium bicarbonate and twice with 100 milliliters of waterand dried over sodium sulfate. Sodium sulfate was subsequently removedby filtration and the nhexane was stripped by rotary evaporation leavinga product residue of 10.8 grams. Infrared spectroscopic analysis of theproduct obtained after nitrooxidation showed the presence of a carbonylfunction and the absence of a peroxynitrate function and the product wasidentified as a mixture of nitroketonized amides including N-(l0-nitro-9-octadecanonyl)-N'-(9- octadecenoyl)-l ,3-diaminopropane,N-(10-nitro-9- octadecanonyl) -N-(9-octadecenoyl)-1,3- diaminopropane,N-(9-nitro-l0-octadecanonyl)-N-(9- octadecenoyl)-l ,3-diaminopropane,N-(9-nitro-10- octadecanonyl)-N-(9-octadecenoyl)-1,3- diaminopropane,N-(9-octadecenyl)-N l0-nitro-9- octadecanonoyl)-1,3-diaminopropane, N-(9- octadecenyl)-N-( l 0-nitro-9-octadecanonoyl)-l ,3- diaminopropane,N-(9-octadecenyl)-N'-(9-nitro-10- octadecanonoyl)-l ,3-diaminopropaneand N-(9- octadecenyl)-N-( 9-nitrol 0-octadecanonoyl)-l ,3-diaminopropane.

EXAMPLE 11 Example I was repeated employing 14.7 grams toluene as theinert solvent and simultaneously contacting the solution with oxygenintroduced at the rate of 60.8 milliliters per minute and dinitrogentetroxide at the rate of 0.0086 moles per minute for 2.9 hours. Aproduct yield of 12.0 grams was obtained and identified as a mixture ofnitroketonized amides as in Example 1.

EXAMPLE 111 To a solution of 25.5 grams (0.05 mole) of N-(9-octadecenyl)-N-octanoyl-1,3-diaminopropane in 300 milliliters ofn-pentane as inert solvent, there was added simultaneously oxygen at therate of 60.8 milliliters per minute and dinitrogen tetroxide at the rateof 0.018 moles per hour for 2.75 hours at 0C. After 2.75 hours 3.1 m1.of liquid dinitrogen tetroxide (0.05 mole) had been transferred to thereaction flask and the solution was purged with oxygen for about onehour. The solution was mixed with water forming an emulsion and pentanewas stripped under vacuum and replaced with ether. The aqueous layer wasseparated and the organic layer was washed three times with 100 ml.portions of water. The organic layer was dried over anhydrous sodiumsulfate, the latter removed by filtration and the solvent stripped fromthe product under vacuum. A yield of 12.9 grams of a product identifiedas a mixture of N-( l0-nitro-9-octadecanonyl)-N-octanoyl-1,3-diaminopropane and N-(9-nitro-l0-octadecanonyl)-N'-octanoyl-1,3-diaminopropane was recovered.

EXAMPLE IV To a solution of 28.3 grams (0.05 mole) of N-(Calkyl-N-(9-octadecenoyl)-1,3-diaminopropane in 300 milliliters of carbontetrachloride as inert solvent, there was added simultaneously oxygen atthe rate of 60.8 ml. per minute and dinitrogen tetroxide at the rate of0.015 moles per hour for 3.2 hours at 0C. After 3.2 hours 3.1 ml. ofliquid dinitrogen tetroxide (0.05 mole) had been transferred to thereaction flask and the solution was purged with oxygen for about onehour. The reaction mixture was washed three times with 100 ml. portionsof water. The organic layer was dried over anhydrous sodium sulfate andthe solvent was stripped from the product under vacuum. A yield of 18.8grams of a product identified as a mixture of N-(C alkyl- N'-(10-nitro-9-octadecanonoyl )-1 ,3-diaminopropane and N-(Calkyl-N'-(9-nitro-10-octadecanonoyl)- 1,3-diaminopropane was recovered.

EXAMPLE V The base fuel employed in the following examples was a premiumgrade gasoline having a research octane number of about 101.5 containing3.0 cc. of tetraethyllead per gallon. This gasoline consisted of about25 percent aromatic hydrocarbons, 14.5 percent olefin hydrocarbons, 60.5percent paraffinic hydrocarbons and boiled in the range of about F. to380F.

A gasoline blend was prepared consisting of the above base fuelcontaining 5 PTB (pound per 1000 barrels of gasoline) of an acid amidemixture of N-(9- octadecenyl)-N'-(9-octadecenoyl)-1 ,3- diaminopropaneand N-(9-octadecenyl)-N-(9- octadecenoyl)-l ,3-diaminopropane. Anothergasoline blend was prepared consisting of the above base fuel containing5 PTB of the nitroketonized acid amide reaction product of Example I.The base fuel and each of the additive-containing gasoline blends weretested and compared for their carburetor detergency' properties in linein preventing the build-up of deposits in the car'bu retor. The gasolineblend containing the nitroketonized acid amide additive was 63 percentmore effective than the base gasoline in preventing the build-up ofdeposits in the carburetor.

EXAMPLE VI To a solution of 14.7 grams (0.025 mole) of a mixture ofN-(9-octadecenyl)-N'-(9-octadecenoyl)-l,3- diaminopropane andN-(9-octadecenyl)-N-(9- octadecenoyl)-l ,3-diaminopropane in 200 ml. ofnhexane as inert solvent, there was added simultaneously oxygen at arate of 60.8 milliliters per minute and dinitrogen tetroxide at the rateof 0.019 mole per hour for 2.7 hours at C. After 2.7 hours, 3.0milliliters of liquid dinitrogen tetroxide (0.05 mole) had beentransferred to the reaction flask and the solution was purged withoxygen for one-half hour. Dimethylformamide (15 ml.) was added to thereaction solution dropwise over a period of 8 minutes at 2 to 5C. Thesolution was mixed with 100 milliliters of 5 percent aqueous sodiumbicarbonate. Hexane was removed from the resulting mixture and replacedwith 400 milliliters of benzene. The aqueous phase was separated and thebenzene layer was washed three times with 200 milliliter portions ofwater. The benzene solution was dried over anhydrous sodium sulfate, thelatter removed by filtration and the solvent stripped from the productunder vacuum. A yield of 7.3 grams of a product composed of a mixture ofN-( l0-nitro-9- octadecanonyl)-N-( -nitro-9 octadecanonoyl)-1,3-diaminopropane, N-( 10-nitro-9-octadecanonyl)-N-(10-nitro-9-octadecanonoyl)-l ,3-diaminopropane, N-(l0-nitro-9-octadecanonyl )-N '-(9-nitrol 0- octadecanonoyl)-l,3-diaminopropane, N-( l0-nitro-9- octadecanonyl )-N-( 9-nitrolO-octadecanonoyl) l ,3- diaminopropane, N-(9-nitro-10-octadecanonyl)-N(10-nitro-9-octadecanonoyl)-l ,3-diaminopropane, N-(9-nitro-10-octadecanonyl)-N-( l0-nitro-9-octadecanonoyl)-l,3-diaminopropane, N-(9-nitro-l0- octadecanonyl )-N-(9-nitrol 0-octadecanonoyl)-l ,3- diaminopropane andN-(9-nitro-lO-octadecanonyl)-N- (9-nitrol 0-octadecanonoyl)-l,3-diaminopropane was obtained.

The base fuel employed in this example was a premium grade gasolinehaving a research octane number of about 102.0 containing 2.86'cc oftetraethyllead per gallon. This gasoline consisted of about 34 percentaromatic hydrocarbons, 9 percent olefinic hydrocarbons, 57 percentparaffinic hydrocarbons and boiled in the range of about 90F. to 380F. Agasoline blend was prepared consisting-of the base fuel containing 32PTB of nitroketonized reaction product recited in Example VI. The basefuel and gasoline blend above were tested for the carburetor anti-icingproperties. The stalling time of base fuel at 0.5 inches of mercury was47 seconds and at 0.9 inches of mercury was 54 seconds. The gasolineblend containing 32 pounds per thousand barrels of the nitroketonizedreaction product at 0.5 inches of mercury was 260 seconds and at 0.9inches of mercury was 274 seconds. f

8 Another gasoline blend was prepared consisting of the above base fueland containing 32 PTB of the nitroketonized acid amide of Example II.The stalling time of this gasoline blend at 0.5 inches of mercury was231 seconds and at 0.9 inches of mercury was 264 seconds.

The anti-rusting properties of the base fuel alone and base fuelscontaining 32 pounds per thousand barrels of the nitroketonized reactionproducts of Examples II and VI respectively were determined employingthe 10 test procedure heretofore described. An examination of thecold-rolled steel strip contacted with the fuel layer in the base fuelrevealed that about 95 percent of the surface area had rusted. Incomparison, the base fuels containing respectively the nitroketonizedproducts of Examples II and VI showed zero percent rusting of thesurface area contacted with the fuel layer.

EXAMPLE VII The nitroketonized product of Example I was evaluated todetermine its affect, if any, on a motor fuels re- 0 search octane atvarious concentrations with the results tabulated below.

Additive In Gasoline Containing 3cc TEL/gallon Research Octane NumberNone (base gasoline) N troketon zed amide 64 PTB Nitroketon zed amide128 PTB Nitroketomzed amide 256 PTB From the tabulation it will be seenthat even at high where R is an alkenyl group having from 4 to carbonatoms, where R and R alternately represent hydrogen and an alkenoylgroup having from 4 to 40 carbon atoms with dinitrogen tetroxide andoxygen at a temperature of from about 35 to C.,

wherein the mole ratio of said acid amide to dinitrogen tetroxide tooxygen is from 112:2 to 1:4:60.

2. A method according to claim 1 wherein said contacting is conducted ata temperature of from 10 to 30C.

3. A method according to claim 1 wherein said acid amide comprises amixture of N-(9-octadecenyl)-N- (9-octadecenoyl)-l,3-diaminopropane andN-(9- octadecenyl)-N-( 9-octadecenoyl)-l ,3- diaminopropane.

4. A method according to claim 1 wherein R, R Or R has from 8 to 22carbon atoms.

5. A method according to claim 1 wherein said nitroketonized amide isN-( l0-nitro-9-octadecanonoyl)- N-(l0-nitro-9-octadecanonoyl)-1,3-diaminopropane.

6. A method according to claim 1 wherein said nitroketonized amide isN-(l0-nitro-9-octadecanonyl)- N-( l0-nitro-9-octadecanonoyl )-l,3-diaminopropane.

7. A method according to claim 1 wherein said nitroketonized amide isN-(9-nitro-l0-octadecanony N'-( 10-nitro-9-octadecanonoyl l,3-diaminopropane.

8. A method according to claim 1 wherein said nitroketonized amide isN-(9-nitro-IO-octadeCanOnyD- N-(9-nitrol 0-octadecanonoyl )-l,3-diaminopropane.

1. A METHOD OF PREPARING A NITROKETONIZED AMIDE WHICH CONSISTSESSENTIALLY OF CONTACTING AN ACID AMIDE OF THE FORMULA:
 1. A method ofpreparing a nitroketonized amide which consists essentially ofcontacting an acid amide of the formula:
 2. A method according to claim1 wherein said contacting is conducted at a temperature of from -10* to30*C.
 3. A method according to claim 1 wherein said acid amide comprisesa mixture of N-(9-octadecenyl)-N''-(9-octadecenoyl)-1,3-diaminopropaneand N-(9-octadecenyl)-N-(9-octadecenoyl)-1,3-diaminopropane.
 4. A methodaccording to claim 1 wherein R1, R2 or R3 has from 8 to 22 carbon atoms.5. A method according to claim 1 wherein said nitroketonized amide isN-(10-nitro-9-octadecanonoyl)-N''-(10-nitro-9-octadecanonoyl)-1,3-diaminopropane.
 6. A method according to claim 1 wherein saidnitroketonized amide isN-(10-nitro-9-octadecanonyl)-N-(10-nitro-9-octadecanonoyl)-1,3-diaminopropane.
 7. A method according to claim 1 wherein saidnitroketonized amide isN-(9-nitro-10-octadecanonyl)-N''-(10-nitro-9-octadecanonoyl)-1,3-diaminopropane.